EP3271429B1 - Compositions durcissables - Google Patents

Compositions durcissables Download PDF

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Publication number
EP3271429B1
EP3271429B1 EP16741403.6A EP16741403A EP3271429B1 EP 3271429 B1 EP3271429 B1 EP 3271429B1 EP 16741403 A EP16741403 A EP 16741403A EP 3271429 B1 EP3271429 B1 EP 3271429B1
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Prior art keywords
hours
less
viscosity
ageing
epoxy resin
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German (de)
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EP3271429A1 (fr
Inventor
Hamed Lakrout
Katherine Clement
Maurice J. Marks
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Blue Cube IP LLC
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Blue Cube IP LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present disclosure relates to a heat stable, radiation curable epoxy resin composition useful, for example, in photosensitive inkjet ink applications.
  • UV inkjet inks are acrylate-based formulations with high viscosity (e.g., greater than [>] 50 millipascal-second [mP-s] at 25 °C). These inkjet inks need special printheads with heating elements to heat the ink formulation and simultaneously lower the viscosity of the ink formulation during jetting.
  • Epoxy-based UV inkjet inks are also known in the art. At high temperature (e.g., > 40 °C), acrylate-based and epoxy-based inks can gel; and gelling can clog printhead channels and thus render the printheads inoperable.
  • Heat stability e.g., exhibiting little to no change in viscosity
  • a long shelf life e.g., no change in properties for 6-12 months
  • Curing of acrylate inks is known to be inhibited by the presence of oxygen in air.
  • a higher level e.g., 5 weight percent [wt %] as opposed to 0.5 wt %) of photoinitiator in an ink formulation is required.
  • Epoxy inks are not inhibited by the presence of oxygen in air, and shrinks less than acrylate inks that lead to improved adhesion. Epoxy inks also have the desirable property of "dark cure", whereby the system continues to react even after the light has ceased. Therefore, an unmet need in the ink industry is a UV ink formulation that is not inhibited by oxygen during curing/ polymerization.
  • inks having a low viscosity and high thermal stability In the ink industry, the development of higher resolution inkjet printheads requires inks having a low viscosity and high thermal stability. Solvents are not preferred in ink jet formulations since the solvents need to be evaporated and release volatile organic compounds into the atmosphere. At present, an ink having a low viscosity is obtained by increasing the temperature of the ink and the printhead. This temperature increase can adversely affect the stability of the ink and the operation of the printer. The use of inks having low viscosity at ambient temperature eliminates the need for the use of heated printheads, improves cost effectiveness, and the environmental sustainability of the printing operation.
  • the prior art fails to describe using a divinylarene dioxide such as divinylbenzene dioxide (DVBDO) in an inkjet ink curable composition having a high heat stability of, for example, above about 40 °C. Therefore, an additional need in the ink industry is for a heat stable pigment UV inkjet ink having an initial viscosity of less than ( ⁇ ) 50 mPa-s.
  • the inks comprise pigments such as cyan or magenta.
  • WO2012009120 describes a photocationically-curable composition including (a) at least one divinylarene dioxide, (b) at least one cationic photoinitiator, and (c) at least one cyclic ester compound; a process for making the curable composition; and a cured product made therefrom; the cured product is described as being useful for various applications including ink formulations.
  • US2011319515 describes a curable divinylarene dioxide resin composition including (a) at least one divinylarene dioxide, (b) at least one cationic photoinitiator, and (c) optionally, at least one pigment material; a process for making the curable divinylarene dioxide resin composition; and a cured divinylarene dioxide resin composition made therefrom; the cured product is described as being useful for various applications including ink formulations.
  • compositions Disclosed herein are heat stable, radiation curable epoxy resin compositions, and methods to prepare and cure these compositions on an article. These compositions are useful as inks.
  • the heat stable, radiation curable epoxy resin compositions comprise: (a) at least one divinylarene dioxide compound; (b) at least one photoinitiator compound selected from triarylsulfonium tris(perfluoroethyl)trifluorophosphate, triarylsulfonium tetrakis(perfluorophenyl)borate, and mixtures thereof, (c) at least one pigment; (d) at least one optional additive; and (e) at least one photosensitizer, wherein the at least one photosensitizer is selected from a group comprising substituted and unsubstituted polynuclear aromatic compounds, substituted and unsubstituted aromatic, heterocyclic compounds, and combinations thereof.
  • the at least one pigment is (i) a cyan pigment, or (ii) a magenta pigment wherein the viscosity, prior to ageing, of the heat stable curable epoxy resin composition is less than about 50 mPa-s at 25 °C.
  • the short term change in viscosity of the composition is less than about 80 percent measured at 25 °C after ageing at 60 °C from about 24 hours to about 72 hours and the long term change in viscosity is less than about 90 percent measured at 25 °C after ageing at 60 °C for at least about 170 hours.
  • the short term change in viscosity of the composition is less than about 50 percent measured at 25 °C after ageing at 60 °C from about 24 hours to about 72 hours and the long term change in viscosity is less than about 50 percent measured at 25 °C after ageing at 60 °C for at least about 105 hours.
  • cured products prepared by curing the heat stable, radiation energy curable epoxy resin composition.
  • processes for preparing a heat stable, energy curable epoxy resin compositions comprise admixing (a) at least one divinylarene dioxide compound; (b) at least one photoinitiator compound selected from triarylsulfonium tris(perfluoroethyl)trifluorophosphate, triarylsulfonium tetrakis(perfluorophenyl)borate, and mixtures thereof; (c) at least one pigment; (d) at least one optional additive; and (e) at least one photosensitizer, wherein the at least one photosensitizer is selected from a group comprising substituted and unsubstituted polynuclear aromatic compounds, substituted and unsubstituted aromatic, heterocyclic compounds, and combinations thereof; wherein the at least one pigment is (i) a cyan pigment based on a phthalocyanine compound, or (ii) a magenta pigment based on a cyclic organic compound
  • the processes comprise applying the epoxy resin composition on an article and then exposing the epoxy resin composition to a curing energy source forming a cured product.
  • thermoinitiator compound selected from triarylsulfonium tris(perfluoroethyl)trifluorophosphate, triarylsulfonium tetrakis(perfluorophenyl)borate, and mixtures thereof;
  • at least one pigment selected from a group comprising substituted and unsubstituted polynuclear aromatic compounds, substituted and unsubstituted aromatic, heterocyclic compounds, and combinations thereof; wherein the at least one pigment is (i) a cyan pigment based on a phthalocyanine compound, or (ii) a magenta pigment based on a cyclic organic compound bearing amino N-H groups; wherein the viscosity,
  • epoxy resin compositions provide many beneficial attributes such as low viscosity ( ⁇ 50 mPa-s at 25°C) prior to ageing and increased thermal stability. After the epoxy resin compositions are applied and cured, the resulting coating provide improved traits such as adhesion to the substrate, water resistance, increased corrosion resistance, smear resistance, and vibrant color.
  • the epoxy resin compositions are heat stable.
  • the heat stable radiation curable epoxy resin composition is a curable composition.
  • the divinylarene dioxide compound, component (a), useful in the present invention of the curable epoxy resin composition comprises at least one divinylarene dioxide compound.
  • the divinylarene dioxide may include, for example, any substituted or unsubstituted arene nucleus bearing one or more vinyl groups in any ring position.
  • the arene portion of the divinylarene dioxide may consist of benzene, substituted benzenes, (substituted) ring-annulated benzenes or homologously bonded (substituted) benzenes, or mixtures thereof.
  • the divinylbenzene portion of the divinylarene dioxide may be ortho, meta, or para isomers or any mixture thereof.
  • Additional substituents may consist of H 2 O 2 -resistant groups including saturated alkyl, aryl, halogen, nitro, isocyanate, or RO- (where R may be a saturated alkyl or aryl).
  • Ring-annulated benzenes may consist of naphthalene, tetrahydronaphthalene, and the like.
  • Homologously bonded (substituted) benzenes may consist of biphenyl, diphenylether, and the like.
  • Non limiting examples of divinylarene dioxide may include one or more substituted divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide, and mixtures thereof.
  • the divinylarene dioxide compound may be a divinylbenzene dioxide (DVBDO).
  • the curable formulation may include two or more conventional epoxy resin compounds wherein at least one of the epoxy resin compounds is a divinylarene dioxide compound.
  • the divinylarene dioxide useful in the curable epoxy resin composition of the present invention may include any of the divinylarene dioxides described in U.S. Patent Patent No. 8,497,387 .
  • each R 1 , R 2 , R 3 and R 4 may independently be hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group; or a H 2 O 2 -resistant group including for example a halogen, a nitro, an isocyanate, or an RO group, wherein R may be an alkyl, aryl or aralkyl; x may be an integer of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an integer of 0 to 6; and z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example, 1,3-phenylene group.
  • R 4 may be a reactive group(s) including epoxide, isocyanate, or any reactive group and Z can be an integer from 0 to 6 depending on the substitution pattern.
  • the divinylarene dioxide useful in the present invention may be produced, for example, by the process described in U.S. Patent No. 8,497,387, by Marks et al. , incorporated herein by reference.
  • the divinylarene dioxides useful in the present invention are disclosed in, for example, U.S. Patent No. 2,924,580 , incorporated herein by reference.
  • the divinylarene dioxide comprises DVBDO, which has a relatively low liquid viscosity and a higher rigidity and crosslink density than conventional epoxy resins.
  • DVBDO may be illustrated by Structure V:
  • the chemical formula of the above DVBDO compound may be as follows: C 10 H 10 O 2 ; the molecular weight of the DVBDO is 162.2; and the elemental analysis of the DVBDO is: C, 74.06; H, 6.21; and O, 19.73 with an epoxide equivalent weight of 81 g/mol.
  • Structure VI below illustrates the meta isomer of DVBDO which may be used in the disclosed resins:
  • Structure VII below illustrates the para isomer of DVBDO, which may be used in the disclosed resins:
  • the present invention includes a DVBDO illustrated by any one of the above Structures individually or as a mixture thereof.
  • Structures VI and VII above show the meta (1,3-DVBDO) isomer and the para (1,4-DVBDO) isomer of DVBDO, respectively.
  • the ortho isomer is rare; and usually DVBDO is mostly produced generally in a range of from 9:1 to 1:9 ratio of meta (Structure VI) to para (Structure VII) isomers.
  • the present invention preferably includes as one embodiment a range of from 6:1 to 1:6 ratio of Structure VI to Structure VII, and in other embodiments the ratio of Structure VI to Structure VII may be from 4:1 to 1:4 or from 2:1 to 1:2.
  • the divinylarene dioxide may contain quantities (such as for example less than 20 wt %) of substituted arenes and/or arene oxides.
  • the amount and structure of the substituted arenes and/or arene oxides mixed with a divinylarene dioxide composition depends on the process used in the preparation of the divinylarene precursor which is used to prepare the divinylarene dioxide.
  • the divinylarene precursor such as divinylbenzene (DVB) may be prepared by the dehydrogenation of diethylbenzene (DEB), and the resultant product composition may contain quantities of ethylvinylbenzene (EVB) and DEB.
  • the EVB present in the reaction mixture may react with hydrogen peroxide to produce ethylvinylbenzene oxide while DEB remains unchanged.
  • the presence of ethylvinylbenzene oxide and DEB in the divinylarene dioxide can increase the epoxide equivalent weight of the divinylarene dioxide to a value greater than that of a pure divinylarene dioxide compound.
  • the divinylarene dioxide may comprise a low viscosity liquid epoxy resin.
  • the viscosity of the divinylarene dioxide used may range from 0.001 Pa-s to about 0.1 Pa-s. In various embodiments, the viscosity of the divinylarene dioxide may range from 0.001 Pa-s to about 0.1 Pa-s, from 0.005 Pa-s to about 0.05 Pa-s, and from 0.01 Pa-s to about 0.025 Pa-s at 25 °C.
  • the rigidity property of the divinylarene dioxide is measured by a calculated number of rotational degrees of freedom of the dioxide excluding side chains using the method of Bicerano described in Prediction of Polymer Properties, Dekker, New York, 1993 .
  • the rigidity of the divinylarene dioxide used in the present invention may range generally from 6 to 10 rotational degrees of freedom in one embodiment, from 6 to 9 rotational degrees of freedom in another embodiment, and from 6 to 8 rotational degrees of freedom in still another embodiment.
  • the amount of the at least one divinylarene dioxide compound used in the curable composition may range from 5 wt % to about 90 wt % of the total composition. In various embodiments, the amount of the at least one divinylarene dioxide may range from 5 wt% to about 90 wt%, from 6 wt% to about 50 wt%, from 7 wt% to about 30 wt%, or from 8 wt % to about 20 wt % based on the total weight of the curable composition. If amounts of the at least one divinylarene dioxide is less than 5 wt %, depending on the other components, the composition may not attain a level of crosslinking sufficient to be dry.
  • the at least one photoinitiator compound, component (b) useful in preparing the curable composition of the present invention is selected from triarylsulfonium tris(perfluoroethyl)trifluorophosphate, triarylsulfonium tetrakis(perfluorophenyl)borate, and mixtures thereof.
  • the photoinitiator compounds do not destabilize the dispersion of the pigment in the curable composition.
  • the at least one photoinitiator affects the cure to dryness in a short amount of time.
  • the time to cure to dryness may be less than 600 seconds, less than 300 seconds, and preferably less than about 120 seconds when exposed to less than about 400 mJ, preferably less than about 300 mJ, and most preferably less than about 200 mJ of light.
  • Nonionic cationic photoinitiators such as nitrobenzyl esters, sulfonyl ketones, phenacyl sulfones, triazines, and phenyl disulfones make thermally stable compositions, but upon UV exposure generate sulfonic acids or fluorosulfonic acids, which are not strong enough to cure these compositions to dryness quickly, instead requiring hours to cure.
  • iodonium salt photoinitiators with perfluorophosphate, antimonate or tetrakis(perfluorophenyl)borate counterions generate much stronger perfluorophosphoric, perfluoroantimonic and tetrakis(perfluorophenyl)boric acids which may rapidly cure.
  • the iodonium salts are not stable to heat and are therefore not suitable to produce stable ink formulations.
  • Organic sulfonium salt photoinitiators with perfluorophosphate, perfluoroantimonate, or other anions capable of producing superacids with pKa's of less than about -12, are both thermally stable as well as produce the superacids necessary for rapid cure.
  • sulfonium salts are capable of interacting with dyes or pigments thus causing instability and an increase in viscosity. This instability is worse for sulfonium cations having more than one sulfonium center and particularly severe for those cations with a bridged sulfonium center such as that found in the sulfonium cations based on thianthreniums or thioxanthenes.
  • Non-limiting examples of the low odor sulfonium photoinitiators are 10-biphenyl-4-yl-2-isopropyl-9-oxo-9H-thioxanthen-10-ium hexafluorphosphate (e.g., Omnicat 550 available from IGM Resins) and 9-4-hydroxyethoxy)thianthrenium hexafluorophosphate (e.g., Esacure 1187 available from Lamberti).
  • the instability results when pigments or dyes having basic nitrogen groups are combined with sulfonium salts in which the sulfonium center is accessible. This instability is eliminated by combining active nitrogen pigments only with sulfonium photoinitiators in which the sulfonium center is shielded by a sufficiently large non-nucleophilic anion.
  • the at least one photoinitiator compound useful in preparing the curable composition of the present invention is selected from triarylsulfonium tris(perfluoroethyl)trifluorophosphate, triarylsulfonium tetrakis(perfluorophenyl)borate, and mixtures thereof.
  • the triarylsulfonium cation may comprise any triarylsulfonium cation wherein the three aryl groups are the same or different and may bear alkyl, aryl, substituted aryl groups, and mixtures thereof.
  • the anion A - is selected from tetrakis(pentafluorophenyl)borate, tris(pentafluoroethyl)trifluorophosphate, and mixtures thereof.
  • the photoinitiator may be a commercially available photoinitiator.
  • the photoinitiator compound may be a solid photoinitiator or a liquid photoinitiator, or a combination thereof.
  • Non-limiting examples of commercially available photoinitiators may be triarylsulfonium tris(perfluoroethyl)trifluorophosphate such as 210S available from San Apro; GSID26-1 and Irgacure 290 available from BASF; and mixtures thereof. These photoinitiators may provide stability of magenta and cyan pigment compounds.
  • these solid photoinitiators may be dissolved in a reactive diluent. Table I illustrates some examples of photoinitiators, Table I: Examples of Photoinitiators Compound Features Trade Name Vendor Salt 210S San Apro Salt Irgacure 290 BASF Salt GSID26-1 BASF
  • the at least one photoinitiator may be Ingracure 290 or 210S.
  • the amount of the at least one photoinitiator compound used in the epoxy resin composition may be from 1 wt % to about 10 wt %. In various embodiments, the amount of the at least one photoinitiator compound may be from 1 wt % to about 10 wt %, from 1.25 wt % to about 8 wt %, from 1.75 wt % to about 6 wt %, or from 2 wt % to about 5 wt % based on the total weight of the curable composition. At low concentrations, the cure speed may be adversely affected. At very low levels, the generated acid can be completely neutralized by basic functional groups present on the colorant, especially magenta and cyan pigments consisting of quinacridones and phthalocyanines.
  • the at least one pigment compound, component (c) comprises a pigment dispersion, wherein the dispersion may consist of a pigment compound, and optionally a synergist and/or a dispersant in a reactive carrier.
  • the pigment may include for example a cyan pigment, a magenta pigment, or mixtures thereof.
  • the cyan and magenta pigment compounds useful in the present invention include those described in the Color Index (C.I.), the industry standard for pigment compounds.
  • the at least one pigment may be a cyan pigment.
  • the at least one cyan pigment may include, for example, any one or more of the following pigments, represented by their Color Index (C.I.) designation, Non-limiting examples of cyan pigments may include Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 22, 60, and 64; Disperse Blue 56, 73, 128, 154, 165, 183, 201, 214, 224, 257, 266, 267, 287, and 368; and mixtures thereof. Table II shows some examples of cyan pigments.
  • the at least one pigment may be a magenta pigment.
  • magenta pigments may be, any one or more of the following pigments, represented by their Color Index (C.I.) designation, such as Pigment Violet 19, 23, 29, 30, 37, 40, and 50; Pigment Red 9, 11, 12, 31, 48, 48:2, 49, 52, 53, 57, 88, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, and 240; and Disperse Red 86, 88, 92, 126, 135, 145, 152, 159, 177, 181, 206, 283, and 348.
  • Table III shows some examples of magenta pigments.
  • Non-limiting examples of pigments that have the preferable light fastness quality may include quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindolin organic pigments; and mixtures thereof.
  • the organic pigments comprise pigment particles having an average particle diameter of from about 10 nanometers (nm) to about 200 nm.
  • the particle size of the pigment may be determined utilizing a laser scattering method. Pigments having an average particle diameter less than about 10 nm lowers the light fastness due to the excessively small particle diameter. Conversely, pigments having an average diameter exceeding 200 nm and in some cases exceeding 150 nm lowers dispersion stability in the dispersion solution, whereby the pigments tend to precipitate.
  • the pigment compound comprises a basic nitrogen functionality, particularly amino N-H groups.
  • these pigments may be (i) a cyan pigment based on a phthalocyanine compound, or (ii) a magenta or cyan pigment based on a cyclic organic compound bearing amino N-H groups.
  • Non-limiting examples of preferred pigments may be PB15:4 (Phthalocyanine Blue NCF (29H,31H-phthalocyaninato( 2- )-N29,N30,N31,N32) copper) Phthalo Blue GS, Pigment Blue 60, Disperse Blue 60, Disperse Blue 56 (1,5-Diamino-2-chloro-4,8-dihydroxy-9,10-anthracenedione), PR122, PV19, Disperse Red 60, PR11, PR12, PR31, PR48:2, PR49:1, PR49:2, PR57, PR81, PR81:1, PR257 (117989-29-4; 70833-37-3 C.I. 562700), PR176 (12225-06-8 C.I.
  • PR185 51920-12-8 C.I. 12516
  • PR177 PR88 (Paliogen Red Violet K 4985)
  • PR123 red Indofast Brilliant Scarlet R-6335
  • PR224 (128-69-8 C.I. 71127)
  • PR176 (12225-06-8 C.I.
  • PR2 (Naphthol Red G), PR21 (Pigment Red 21), PR22 (Naphthol red bright), PR38 (Pyrazolone Red), PR48:2 (Calcium Red), PR112 (Naphthol red AS), PR122 (Quinacridone Red), PR123 (Perylene), PR170 (Naphthol red), PR178 (Perylene Red), PR254 (Pyrrole red), PV19 (Quinacridone Violet), PV23 (Permanent violet); and mixtures thereof.
  • the amount of the at least one pigment compound used in the curable composition may range from 0.5 wt % to about 15 wt % based on the total weight of the composition. In various embodiments, the amount of the at least one pigment may range from 0.5 wt % to about 15 wt %, from 0.6 wt% to about 12 wt%, from 0.75 wt% to about 10 wt%, from 1.0 wt% to about 7.5 wt%, or from 1.5 wt% to about 5 wt%. At concentrations above 15 wt % of the pigment, the viscosity of the composition increases rapidly and the level of shading and light absorption in the coating can make achieving complete cure difficult.
  • the curable epoxy resin composition may further comprise at least one additive chosen from another epoxy compound other than the divinylarene dioxide, an oxetane, a filler, a reactive diluent, a flexibilizing agent, a processing agent, and a toughening agent.
  • the curable epoxy resin composition may comprise at least one dispersant compound which may be used to prepare a pigment dispersion.
  • dispersant may be Solsperse 20000, Solsperse 22000, Solsperse 27000, Solsperse 32000, Solsperse 39000, Solsperse 41000, Solsperse 5000, Bykjet 9150, Bykjet 9151, and mixtures thereof.
  • the curable epoxy resin composition may optionally include at least one other epoxy compound other than the divinylarene dioxide to form the epoxy matrix in a final curable formulation.
  • the epoxy compound may include any conventional epoxy compound.
  • the epoxy compound may be, for example, a single epoxy compound used alone; or a combination of two or more epoxy compounds known in the art such as any of the epoxy compounds described in Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Company, New York, 1967, Chapter 2, pages 2-1 to 2-27 , incorporated herein by reference.
  • the second epoxy compound may include cycloaliphatic or aliphatic epoxy compounds such as limonene dioxide, epoxidized linseed oil (ELO), cyclohexene oxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Synasia 06, ERL 4221, Cyracure 6105), bis((3,4-epoxycyclohexyl)methyl)adipate (Synasia 28), styrene oxide, or mixtures thereof.
  • cycloaliphatic or aliphatic epoxy compounds such as limonene dioxide, epoxidized linseed oil (ELO), cyclohexene oxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Synasia 06, ERL 4221, Cyracure 6105), bis((3,4-epoxycyclohex
  • the amount of the second epoxy compound may be from 0 wt % to about 60 wt % based on the total weight of the composition. In various embodiments, the amount of the second epoxy resin compound may range from 0 wt % to about 60 wt %, from 0.01 wt % to about 50 wt %, and from about 4 wt % to about 40 wt % based on the total weight of the curable composition.
  • the curable epoxy resin composition may optionally include at least one cationically polymerizable monomer, as a reactive diluent (for example, for the purpose of decreasing crosslink density, reducing viscosity, and increasing flexibility).
  • cationically polymerizable monomers may be aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, cationically polymerizable nitrogen-containing monomers, and mixtures thereof.
  • Examples of the aliphatic monovinyl ethers may include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, 2-acetoxyethyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether, 2-acryloyloxyethyl vinyl ether, and mixtures thereof.
  • aromatic monovinyl ethers may include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, p-methoxyvinyl ether, and mixtures thereof.
  • polyfunctional vinyl ether may include triethylene glycol divinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, hydroquinone divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, and mixtures thereof.
  • styrenes may include styrene, a-methylstyrene, p-methyoxystyrene, p-tert-butoxystyrene, and mixtures thereof.
  • cationically polymerizable nitrogen-containing monomers may include N-vinylcarbazole, N-vinylpyrrolidone, and mixtures thereof.
  • the amount of the at least one vinyl ether compound used in the curable composition may be from 0 wt % to about 60 wt %. In various embodiments, the amount of the at least one vinyl ether compound used in the curable composition may range from 0 wt % to about 60 wt %, from 1 wt % to about 55 wt %, or from 5 wt % to about 50 wt % based on the total weight of the components in the curable composition.
  • the reactive diluent may comprises an oxetane, a cyclic organic carbonate, a polyol, a lactone, or combinations thereof.
  • these diluents may be Toagosei oxetane 101, oxetane 212, oxetane 221, a cyclic carbonate such as propylene carbonate, a polyol, such as diethylene glycol, triethylene glycol, polycaprolactones such as CAPA, polytetrahydrofurans such as Terathane 250, Terathane 650, Terathane 1000, and combinations thereof.
  • the amount of diluent when used in the curable composition may be for example, from 0 wt % to about 50 wt % in one embodiment, from about 0.01 wt % to about 45 wt % in another embodiment; from about 0.1 wt % to about 40 wt % in still another embodiment; and from about 1 wt % to about 35 wt % in yet another embodiment.
  • a photosensitizer as a modifier agent, may be added to the formulation for the purpose of altering UV wavelengths which can be used for cure.
  • the at least one photosensitizer, component (e) is selected from a group comprising substituted and unsubstituted polynuclear aromatic compounds, substituted and unsubstituted aromatic, heterocyclic compounds, and combinations thereof.
  • Non-limiting examples of photosensitizer may include 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene; and mixtures thereof.
  • the amount of the photosensitizer used in the curable composition can and will vary depending on the end use of the curable composition and the cure speed desired. For example, as one illustrative embodiment, when cure is desired to occur using UV LED's at a wavelength such as 390 nm at which the sulfonium photoinitiator is not reactive, a photosensitizer such as 9,10-diethoxyanthracene can be added.
  • the amount of photosensitizer in the composition may be from 0 wt % to about 4 wt %.
  • the amount of photosensitizer in the composition may be from 0 wt % to about 4 wt %, from 0.01 wt % to about 3 wt %; and from 0.5 wt % to about 2 wt % based on the total weight of the components in the curable composition.
  • a modifier may be added to the formulation for the purpose of altering the surface tension or haptic properties.
  • Non-limiting examples of the surface tension/haptic property modifiers may be BYK 378, BYK 307, Dow Corning 204SL, and mixtures thereof.
  • the amount of the modifier used in the curable composition can and will depending on the end use of the curable composition.
  • the amount of modifier in the composition may be from 0 wt % to about 4 wt %.
  • the amount of modifier in the composition may be from 0 wt % to about 4 wt %, from 0.01 wt % to about 2 wt % in and from 0.1 wt % to about 1 wt % based on the weight of the curable composition.
  • optional additives may be introduced to the curable composition.
  • These optional additives may include compounds that are normally used in resin formulations known to those skilled in the art for preparing curable compositions and thermosets.
  • Non-limiting examples of the optional components may comprise compounds that can be added to the composition to enhance application properties (e.g., surface tension modifiers or flow aids), reliability properties (e.g., adhesion promoters) the reaction rate, the selectivity of the reaction, and/or the catalyst lifetime.
  • Other optional components that may be added to the curable composition of the present invention may include toughening agents, flow modifiers, adhesion promoters, stabilizers, flexibilizing agent, a processing aide, plasticizers, and mixtures thereof.
  • the amount of the optional components used in the curable composition of the present invention can and will vary depending on the end use of the curable composition.
  • the amount of the optional components when used, may be from 0 wt % to about 50 wt %.
  • the amount of the optional components may be from 0 wt % to about 50 wt %, from about 0.1 wt % to 40 wt %, from 1 wt % to about 30 wt % and from 2 wt % to about 20 wt % based on the the weight of the curable composition.
  • the heat stable, epoxy resin curable composition before curing, is a liquid.
  • the curable composition exhibits a low viscosity ( ⁇ 50 mPa•s at 25°C).
  • the composition being of low viscosity facilitates the processing of the low viscosity formulation, particularly when the formulation is used in inkjet ink applications.
  • a low viscosity ink formulation of the present invention generally may exhibit a viscosity at 25°C of less than or equal to about 50 mPa•s, less than about 40 mPa•s, less than about 30 mPa•s, less than about 20 mPa•s and less than about 10 mPa•s.
  • the low viscosity composition of the present invention may exhibit a viscosity of greater than about 2 mPa•s, greater than about 4 mPa•s, and greater than about 5 mPa•s.
  • the viscosity of the curable composition may exhibit a viscosity of from 2 mPa•s to about 50 mPa•s, from 4 mPa•s to about 40 mPa•s, and from 5 mPa•s to about 30 mPa•s.
  • the curable composition exhibits heat stability sufficient to provide the benefit of facilitating the processing of the heat stable formulation, particularly when the formulation is used in inkjet ink applications.
  • the short-term change in viscosity and the long-term change in viscosity (measured at 25 °C) of the curable composition containing the cyan pigment and the magenta pigment (after ageing at 60 °C) as described above provides a heat stable ink formulation of the present invention that advantageously can be processed through inkjet process without degradation of the ink by heat.
  • the short term change (between about 24 hours and about 72 hours) in cyan's ink viscosity (measured at 25 °C) after ageing at 60 °C is less than 80 %.
  • the short term change in cyan' s ink viscosity (measured at 25 °C) may be less 80%, less than 75%, and less than about 70 %.
  • the long term change (about at least 170 hours) in viscosity (measured at 25 °C) of the cyan ink after ageing at 60 °C is less than about 90 %.
  • the long term change in the viscosity (measured at 25 °C) may be less than 90%, less than 80%, and less than about 70 %.
  • the short term change (between about 24 hours and about 72 hours) in magenta's ink viscosity (measured at 25 °C) after ageing at 60 °C is less than 50 %.
  • the short term change in magenta' s ink viscosity (measured at 25 °C) may be less 50%, less than 30%, and less than about 10 %.
  • the long term change (about at least 105 hours) in viscosity (measured at 25 °C) of the magenta ink after ageing at 60 °C for at least 105 hours is less than about 50 %.
  • the long term change in the viscosity (measured at 25 °C) may be less than 50%, less than 30%, and less than about 10 %.
  • low viscosity, heat stable ink formulation advantageously can be processed through a wider range of inkjet print heads at higher temperatures.
  • low viscosity, heat stable ink formulation of the present invention can be processed through inkjet print head temperatures of from about 0 °C to about 60 °C.
  • the processes for preparing the heat stable UV curable epoxy resin composition includes admixing (a) at least one divinylarene dioxide compound; (b) at least one photoinitiator compound selected from triarylsulfonium tris(perfluoroethyl)trifluorophosphate, triarylsulfonium tetrakis(perfluorophenyl)borate, and mixtures thereof; (c) at least one pigment compound; (d) at least one optional additive; and (e) at least one photosensitizer, wherein the at least one photosensitizer is selected from a group comprising substituted and unsubstituted polynuclear aromatic compounds, substituted and unsubstituted aromatic, heterocyclic compounds, and combinations thereof; wherein the at least one pigment is (i) a cyan pigment based on a phthalocyanine compound, or (ii) a magenta pigment based on a cyclic organic compound bearing amino N-H groups; wherein the viscos
  • the preparation of the curable epoxy resin composition may be achieved by blending, in known mixing equipment, the divinylarene dioxide compound, the photoinitiator compound, the pigment, and optionally any other desirable additives in any order.
  • any of the above-mentioned optional additives for example a second epoxy resin or a vinyl ether, may be added to the composition during the mixing or prior to the mixing to form the composition.
  • All the compounds of the curable epoxy resin composition may be mixed and dispersed at a temperature enabling the preparation of an effective UV curable epoxy resin composition having the desired balance of properties for a particular application.
  • the temperature during the mixing of all components may range from 0°C to about 50°C.
  • the temperature during the mixing of all the components from 0°C to about 50°C, from 10°C to about 40°C, or from 20°C to about 30°C.
  • the temperature during the mixing of all the components may be about room temperature (-23 °C). Lower mixing temperatures may help to minimize side reactions and may maximize the pot life of the composition.
  • the mixing may be typically performed under ambient pressure.
  • the reaction may also be conducted under an inert atmosphere, for example, under nitrogen, argon, or helium.
  • the preparation of the curable epoxy resin composition, and/or any of the steps thereof, may be a batch or a continuous process.
  • the mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.
  • the processes comprise providing a curable, heat stable epoxy resin composition, which is detailed above, and exposing the curable epoxy resin composition to a curing energy source to form the cured epoxy resin coating.
  • the curable heat stable epoxy resin composition is applied to at least a portion of a surface of an article to be coated, prior to subjecting it to an energy source for curing.
  • Suitable heat stable curable epoxy resin compositions are described above.
  • an article comprising a cured or uncured low viscosity epoxy resin composition adhering to at least one portion of the substrate.
  • the article in broad terms, may be defined as a material wherein the heat stable curable epoxy resin composition is initially applied. The composition then adheres to at least a portion of at least one surface of the substrate.
  • the curable epoxy resin composition may be cured at a exposing the composition to a curing energy source to form a thermoset or cured composition such that the coating bonds to the substrate.
  • the article may be any material that can withstand the curing energy to form a cured coating.
  • the article may be a metal.
  • the article, as defined herein, may be a single metal or an alloy of various metals. Non-limiting examples of these metals include cast iron, aluminum, tin, brass, steel, copper, zinc aluminum alloy, nickel, or combinations thereof.
  • the substrate may be a cellulose product.
  • cellulose products may be paper, paperboard, paper cardstock, cardboard, and wood.
  • the substrate may be a plastic.
  • plastics may be bakelite, polyester, polyethylene terephthalate, polyethylene, high density polyethylene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyamides (Nylon), acrylonitrile butadiene styrene, polycarbonates, polyurethanes, and combinations thereof.
  • the article may be a fabric or a textile.
  • fabrics may be wool, canvas, cotton, Gore-Tex, hemp, Kevlar, knit, lace, lambswool, leather, linen, neoprene, Nomex, nylon, polyester, rayon, silk, suede, velour, velvet, vinyl coated polyester, and combinations thereof.
  • the article may be in various configurations.
  • Non-limiting configuration examples of the article may be a roll, a coil, a plate, a sheet, a tube, or a pipe.
  • the configuration of the article may be of various dimensions, shapes, thicknesses, and weights.
  • the article may be paper, a fabric, or a textile.
  • the process further comprises applying the curable epoxy resin composition to a portion of at least one surface of an article.
  • Suitable articles are detailed above.
  • Application of the curable coating composition may be applied through various means.
  • the coating composition may be applied using a drawdown bar, a roller, a knife, a paint brush, a sprayer, dipping, an inkjet device, or other methods known to the skilled artisan.
  • more than one application of the coating composition may be applied forming a multi-layered coating.
  • the curable coating composition may be applied to one or more surfaces of the article to be coated.
  • One preferred application of these curable epoxy resin composition may be ink jet or an inkjet device. The composition may be loaded into an ink jet cartridge, and then applied to an article.
  • the process further comprises curing the curable epoxy resin composition to a portion of at least one surface of an article.
  • the heat stable curable compositions may be cured by exposing the composition to a curing energy source to form a cured composition or thermoset.
  • These curable compositions may include various coatings and more specifically, inkjet ink coatings.
  • curing energy the composition may be cured by various energy means.
  • the various energy means may include thermal means, electron beam means, and UV means.
  • a UV curable inkjet ink formulation may be processed in accordance with the procedure described in Hudd, Alan, p.5, Chemistry of Inkjet inks Edited by: Magdassi, Shlomo ⁇ 2010 World Scientific .
  • the curable composition may be cured using a UV lamp or source with multiple wavelengths such as with a metal halide light source or a unique narrow wavelength distribution provided by a light-emitting diode (LED) at a UV wavelength of generally from about 190 nm to about 450 nm.
  • the UV wavelength may be from 190 nm to about 450 nm, from 200 nm to about 425 nm, or from 210 nm to about 400 nm.
  • the curing energy the curable composition may be chosen between 20mJ/cm 2 to about 1000 mJ/cm 2 .
  • the curing energy may be between 20mJ/cm 2 to about 1000 mJ/cm 2 , between 30 mJ/cm 2 to about 800mJ/cm 2 , between 40 mJ/cm 2 to about 500 mJ/cm 2 , and between 50 mJ/cm 2 to about 250 mJ/cm 2 .
  • the cure speed of a curable composition can and will vary depending on the level of photoinitiator used and the level of curing energy to which the curable composition is exposed. High levels of either are undesirable, with the level of photoinitiator generally limited to 5 % or less of contained photoinitiator. Faster cure speeds are preferred with cure speeds to a dry surface of generally less than 10 s desired. Cure speed to a surface that does not mar when rubbed can take longer but is generally preferred to be less than 2 minutes (min). Generally, the cure speed for curing the curable composition to a non-marrable finish for photoinitiator levels of 5 % or less and energy levels of 250 mJ or less may be between 2 s to about 120 seconds.
  • the cure speed for the curing the curable composition composition to a non-marrable finish for photoinitiator levels of 5 % or less and energy levels of 250 mJ may be between 2 s and 120 s, between 2 seconds to about 60 s, and between about 2 s to about 30 s.
  • the UV cured product (i.e., the cross-linked product made from the curable composition) of the present invention shows several improved properties over conventional UV epoxy cured resins.
  • the cured product of the present invention may advantageously have increased pigment content, increased corrosion resistance, water resistance, and greater adhesion to the article.
  • the cured product when the inkjet ink formulation is cured as the ink is disposed on the surface of a substrate such as a paper product, the cured product has the following properties such as dry to touch, smear resistance, adhesion, and vibrant color.
  • composition of the present invention may be used to provide manufacturing coatings, such as inks, and in particular UV inks; and paints.
  • the curable composition of the present invention may be used to manufacture a cured thermoset product such as coatings in UV cure applications, adhesives, and marine repair.
  • the composition may be used to manufacture 3-dimensional objects for rapid prototyping.
  • the curable composition can be used to prepare UV cure formulations for inks and coatings.
  • the inkjet ink formulations of the present invention exhibit a combination of properties that deliver a unique readily processable formulation in ink applications.
  • Each one of the following pigments is delivered as a 25 % dispersion in a carrier, either vinyl ether such as TEGDVE (“carrier-TEGDVE”), or as a blend of vinyl ether and cycloaliphatic epoxy resin:
  • the viscosity of the formulation was measured on a stress control rheometer TA Instruments AR2000 equipped with a 60 millimeter (mm) diameter flat stainless steel upper plate and a bottom Peltier plate assembly controlling both the temperature of the liquid sample and the normal force acting on the surface of the Peltier plate. About 0.5 milliliter (mL) of the formulation was deposited on the bottom plate before the top plate was lowered onto the liquid formulation until a gap of 100 microns (p) between the two plates was achieved. The top plate was then rotated at a shear rate of 10 s-1 while the temperature of the bottom plate was maintained at 25 °C. Viscosity was automatically calculated using software by TA Instruments and reported in millipascals seconds (mPa-s).
  • Ink compositions were prepared by weighing a dry photoinitiator into DVBDO or other epoxy. After the photoinitiator dissolved in the DVBDO, vinyl ethers and cycloaliphatic epoxy were added to the solution of photoinitiator and DVBDO; and the solution was mixed by shaking. A pigment dispersion was then added to the resulting mixture; and the mixture was made homogeneous by either shaking or rolling for several minutes. When and if the photoinitiator was supplied as a liquid in a carrier such as propylene carbonate, the photoinitiator/carrier was added to the above mixture after the other components but before the pigment dispersion.
  • a carrier such as propylene carbonate
  • the dry photosensitizer was weighed in first and dissolved in vinyl ether.
  • the inks were then filtered through a 1 t glass fiber filter and stored in opaque containers.
  • the components of each ink formulation are expressed as their wt %.
  • Ink compositions were stored at 60 °C and their viscosity at 25 °C was measured periodically after 24 - 72 hours (hr), herein referred to as “short term”, and thereafter periodically for at least 100 hr and up to 483 hr, herein referred to as "long term”.
  • the thermal stability of the ink is measured by the change in viscosity after the short and/or the long term tests versus the initial viscosity and by the percentage increase in the viscosity between the short and/or the long term tests versus the initial viscosity. Both lower viscosity change and lower % viscosity change represent a better thermal stability of the ink.
  • Examples 1 - 6 described in Table IV were prepared using the "General Ink Preparation Procedure" as described above and using a phthalocyanine type cyan pigment PB15:4 and a triarylsulfonium tetrakis(pentafluorophenyl)borate photoinitiator Irgacure 290.
  • Examples 1 - 6 demonstrate cyan ink formulations having an initial viscosity of ⁇ 30 mPa-s at 25 °C; having a short term thermal stability of ⁇ 40 %; and having a long term stability of ⁇ 30 %.
  • Comparative Examples A and B described in Table V were prepared as described above in Examples 1 - 6 using a phthalocyanine type cyan pigment PB15:4 and a triarylsulfonium hexafluorophosphate photoinitiator CPI 6992.
  • Comparative Examples A and B show that such formulations similar to the formulations of Examples 1 - 6 have an initial viscosity of ⁇ 30 mPa-s at 25 °C. When a different photoinitiator is used, the formulations have a short term thermal stability of > 130 %.
  • Examples 7 - 14 described in Table VI were prepared as described above in Examples 1 - 6 using a phthalocyanine type cyan pigment PB15:4 and either a triarylsulfonium tetrakis(pentafluorophenyl)borate photoinitiator Irgacure 290 or a triarylsulfonium trifluorotris(pentafluoroethyl)phosphate photoinitiator CPI 210S.
  • Examples 7-14 demonstrate cyan ink formulations having an initial viscosity ⁇ 10 mPa-s at 25°C and having a short term thermal stability of ⁇ 70 % change in viscosity and a long term thermal stability of ⁇ 70 % change in viscosity. For instance, Example 14 shows greatly improved stability as compared to the use of hexafluorphosphate or hexafluoroantimonate.
  • Comparative Examples C-G described in Table VII were prepared as described above in Examples 1 - 6 using a phthalocyanine type cyan pigment PB15:4 and either a triarylsulfonium hexafluorophosphate photoinitiator such as CPI 6992 or CP1100P, or a bridged triarylsulfonium hexafluorophosphate photoinitiator such as Esacure 1187 or Omnicat 650, or a triarylsulfonium triflate.
  • a triarylsulfonium hexafluorophosphate photoinitiator such as CPI 6992 or CP1100P
  • a bridged triarylsulfonium hexafluorophosphate photoinitiator such as Esacure 1187 or Omnicat 650
  • a triarylsulfonium triflate such as Esacure 1187 or Omnicat 650
  • Comparative Example C shows a formulation similar to those of Examples 1 - 6 having an initial viscosity ⁇ 10 mPa-s at 25 °C except that the formulation of Comparative Example C uses a different photoinitiator; and has a short term thermal stability of 90 % and a long term thermal stability of > 100 %.
  • Comparative Examples D - G show formulations similar to those of Examples 1 - 6 except that the Comparative Examples D-G use different photoinitiators; and do not have an initial viscosity ⁇ 10 mPa-s at 25 °C.
  • the concentration of photoinitiator was limited to 3 wt % because of the photoinitiator's limited solubility.
  • Examples 15 - 17 described in Table VIII were prepared as described above in Examples 1 - 6 using quinacridone type magenta pigments PR122 and PV19 and a triarylsulfonium tetrakis(pentafluorophenyl)borate photoinitiator Irgacure 290.
  • Examples 15 - 17 describe magenta ink formulations that have an initial viscosity of ⁇ 30 mPa-s at 25 °C; and that have a long term stability of ⁇ 10 %.
  • Comparative Examples H - L described in Table IX were prepared as described above in Examples 1 - 6 using a quinacridone type magenta pigment PR122 and either a triarylsulfonium hexafluorophosphate photoinitiator as CPI 6992, Esacure 1187, Double Cure 1190, Double Cure 1176, Irgacure 270, or Ningbo triarylsulfonium hexafluoroantimonate.
  • a quinacridone type magenta pigment PR122 and either a triarylsulfonium hexafluorophosphate photoinitiator as CPI 6992, Esacure 1187, Double Cure 1190, Double Cure 1176, Irgacure 270, or Ningbo triarylsulfonium hexafluoroantimonate.
  • Comparative Examples H - L show that formulations similar to those of Examples 15 - 17 having an initial viscosity of ⁇ 30 mPa-s at 25 °C but using different photoinitiators have a long term thermal stability of > 120 %.
  • Examples 18 -21 described in Table X were prepared as described above in Examples 1 - 6 using quinacridone type magenta pigments PR122 and PV19 and either a triarylsulfonium tetrakis(pentafluorophenyl)borate photoinitiator Irgacure 290, or a triarylsulfonium trifluoro-tris(pentafluoroethyl)phosphate photoinitiator CPI 210S.
  • Examples 18-21 describe magenta ink formulations that have an initial viscosity ⁇ 10 mPa-s at 25°C; and that have a short term thermal stability of ⁇ 10 % and a long term stability of ⁇ 10 %.
  • Comparative Examples H-L described in Table XI were prepared as described above in Examples 1-6 using a quinacridone type magenta pigment PR122 or PV19 and either a triarylsulfonium hexafluorophosphate photoinitiator such as CPI 6992, Esacure 1187, or CPI 100P.
  • Comparative Examples M-O describe formulations similar to those of Examples 18 - 21 having an initial viscosity ⁇ 10 mPa-s at 25 °C; except that the formulations use a different photoinitiator and have a short term thermal stability of > 90 % and a long term thermal stability > 75 %.
  • Comparative Examples P and Q describe formulations similar to those of Examples 18-22 except that the formulations use different photoinitiators; and do not have an initial viscosity ⁇ 10 mPa-s at 25 °C.

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Claims (15)

  1. Composition de résine époxy thermostable durcissable par rayonnement permettant la préparation d'une composition d'encre comprenant :
    (a) au moins un composé de dioxyde de divinylarène ;
    (b) au moins un composé photoinitiateur choisi parmi le tris(perfluoroéthyl)trifluorophosphate de triarylsulfonium, le tétrakis(perfluorophényl)borate de triarylsulfonium et leurs mélanges ;
    (c) au moins un pigment ;
    (d) au moins un additif supplémentaire ; et
    (e) au moins un photosensibilisateur, ledit au moins un photosensibilisateur étant choisi dans le groupe comprenant les composés aromatiques polynucléaires substitués et non substitués, les composés hétérocycliques aromatiques substitués et non substitués et leurs combinaisons ;
    ledit au moins un pigment étant (i) un pigment cyan, ou (ii) un pigment magenta ;
    la viscosité, avant vieillissement, de la composition de résine époxy thermostable durcissable étant inférieure à environ 50 mPa.s à 25°C ;
    le changement à court terme de viscosité mesuré à 25°C de l'encre cyan après vieillissement à 60°C d'environ 24 heures à environ 72 heures étant inférieur à environ 80 pour cent et le changement à long terme de viscosité mesuré à 25°C de l'encre cyan après vieillissement à 60°C pendant au moins environ 170 heures étant inférieur à environ 90 pour cent ; et
    le changement à court terme de viscosité mesuré à 25°C de l'encre magenta après vieillissement à 60°C d'environ 24 heures à environ 72 heures étant inférieur à environ 50 pour cent et le changement à long terme de viscosité mesuré à 25°C de l'encre magenta après vieillissement à 60°C pendant au moins environ 105 heures étant inférieur à environ 50 pour cent.
  2. Composition de résine époxy durcissable selon la revendication 1, ladite viscosité de la composition de résine époxy thermostable durcissable valant d'environ 2 mPa.s à environ 50 mPa.s mesurée à 25°C ;
    ledit changement à court terme de viscosité mesuré à 25°C de l'encre cyan après vieillissement à 60°C d'environ 24 heures à environ 72 heures étant inférieur à environ 70 pour cent et ledit changement à long terme de viscosité mesuré à 25°C de l'encre cyan après vieillissement à 60°C pendant au moins environ 170 heures étant inférieur à environ 70 pour cent ; et
    ledit changement à court terme de viscosité mesuré à 25°C de l'encre magenta après vieillissement à 60°C de 24 heures à 72 heures étant inférieur à environ 10 pour cent et ledit changement à long terme de viscosité mesuré à 25°C de l'encre magenta après vieillissement à 60°C pendant au moins environ 105 heures étant inférieur à environ 10 pour cent.
  3. Composition de résine époxy durcissable selon la revendication 1 ou 2, la viscosité de la composition durcissable mesurée à 25°C valant d'environ 2 mPa.s à environ 25 mPa.s.
  4. Composition de résine époxy durcissable selon l'une quelconque des revendications 1 à 3, ledit au moins un composé de dioxyde de divinylarène étant choisi dans le groupe comprenant le dioxyde de divinylbenzène substitué, le dioxyde de divinylnaphtalène, le dioxyde de divinylbiphényle, le dioxyde de divinyldiphényléther et les combinaisons de ceux-ci.
  5. Composition de résine époxy durcissable selon l'une quelconque des revendications 1 à 4, ledit au moins un composé de dioxyde de divinylarène étant une résine de dioxyde de divinylbenzène.
  6. Composition de résine époxy durcissable selon l'une quelconque des revendications 1 à 5, ledit au moins un composé de pigment étant choisi dans le groupe constitué par PB15:4, PR122, PV19 et leurs mélanges.
  7. Composition durcissable selon l'une quelconque des revendications 1 à 6, ladite composition comprenant au moins un composé d'éther vinylique.
  8. Composition durcissable selon l'une quelconque des revendications 1 à 7, ledit éther vinylique étant l'éther divinylique de butanediol, l'éther divinylique de diéthylène glycol, l'éther divinylique de triéthylène glycol ; ou leurs mélanges.
  9. Composition durcissable selon l'une quelconque des revendications 1 à 8, ladite composition comprenant au moins un composé d'époxyde, différent du dioxyde de divinylarène.
  10. Composition durcissable selon l'une quelconque des revendications 1 à 9 comprenant une composition durcissable d'encre pour jet d'encre thermostable.
  11. Procédé de préparation d'une composition de résine époxy thermostable durcissable par UV permettant la préparation d'une composition d'encre comprenant le mélange de :
    (a) au moins un composé de dioxyde de divinylarène ;
    (b) au moins un composé photoinitiateur choisi parmi le tris(perfluoroéthyl)trifluorophosphate de triarylsulfonium, le tétrakis(perfluorophényl)borate de triarylsulfonium et leurs mélanges ;
    (c) au moins un pigment ;
    (d) au moins un additif supplémentaire ; et
    (e) au moins un photosensibilisateur, ledit au moins un photosensibilisateur étant choisi dans le groupe comprenant les composés aromatiques polynucléaires substitués et non substitués, les composés hétérocycliques aromatiques substitués et non substitués et leurs combinaisons ;
    ledit au moins un pigment étant (i) un pigment cyan à base d'un composé de phtalocyanine, ou (ii) un pigment magenta à base d'un composé organique cyclique portant des groupes amino N-H;
    la viscosité, avant vieillissement, de la composition de résine époxy thermostable durcissable étant inférieure à environ 50 mPa.s à 25°C ;
    le changement à court terme de viscosité mesuré à 25°C de l'encre cyan après vieillissement à 60°C d'environ 24 heures à environ 72 heures étant inférieur à environ 80 pour cent et le changement à long terme de viscosité mesuré à 25°C de l'encre cyan après vieillissement à 60°C pendant au moins environ 170 heures étant inférieur à environ 90 pour cent ; et
    le changement à court terme de viscosité mesuré à 25°C de l'encre magenta après vieillissement à 60°C d'environ 24 heures à environ 72 heures étant inférieur à environ 50 pour cent et le changement à long terme de viscosité mesuré à 25°C de l'encre magenta après vieillissement à 60°C pendant au moins environ 105 heures étant inférieur à environ 50 pour cent.
  12. Procédé selon la revendication 11, lesdits composants étant mélangés entre 0°C à 50 °C.
  13. Produit durci préparé par durcissement de la composition de résine époxy durcissable selon l'une quelconque des revendications 1 à 10.
  14. Produit durci selon la revendication 13, ledit produit comprenant un revêtement d'encre pour jet d'encre.
  15. Produit durci selon l'une quelconque des revendications 13 ou 14, ledit produit comprenant un produit thermodurci.
EP16741403.6A 2015-03-20 2016-03-17 Compositions durcissables Active EP3271429B1 (fr)

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US201562135748P 2015-03-20 2015-03-20
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JP7160532B2 (ja) * 2015-03-20 2022-10-25 ブルー キューブ アイピー エルエルシー 硬化性組成物
KR102253501B1 (ko) * 2018-09-28 2021-05-18 주식회사 엘지화학 밀봉재 조성물
US20230322998A1 (en) * 2020-06-02 2023-10-12 Blue Cube Ip Llc Photo-curable resin composition for use in stereolithography
US11352514B1 (en) 2021-06-09 2022-06-07 Altana New Technologies Gmbh Dual-curable inkjet composition

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US2924580A (en) 1957-08-08 1960-02-09 Union Carbide Corp Divinyl benzene dioxide compositions
JPS62290769A (ja) * 1986-06-11 1987-12-17 Hitachi Chem Co Ltd 紫外線硬化型マ−キング組成物
EP0878472A1 (fr) * 1997-05-16 1998-11-18 National Starch and Chemical Investment Holding Corporation Monomères époxydes réactifs, durchissables cationiquement par radiation ou thermiquement et compositions les contenant
US6350792B1 (en) * 2000-07-13 2002-02-26 Suncolor Corporation Radiation-curable compositions and cured articles
US7309122B2 (en) * 2003-06-24 2007-12-18 Konica Minolta Medical & Graphic, Inc. Method for storing cationic polymerizable composition and container for using thereof
JP4646103B2 (ja) * 2003-06-24 2011-03-09 コニカミノルタエムジー株式会社 カチオン重合性組成物の保存方法及びそれに用いる保存容器
EP2043865B1 (fr) * 2006-07-13 2010-03-31 Telecom Italia S.p.A. Cartouche pour jets d'encre présentant une couche faite d'une composition de résines durcissables
JP4789725B2 (ja) * 2006-07-14 2011-10-12 日本化薬株式会社 感光性樹脂組成物、その積層体、その硬化物及び該組成物を用いたパターン形成方法
CN104529946A (zh) 2008-12-30 2015-04-22 陶氏环球技术有限责任公司 用于制备二乙烯基芳烃二氧化物的方法
EP2585513A2 (fr) * 2010-06-28 2013-05-01 Dow Global Technologies LLC Compositions de résines durcissables
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US8865392B2 (en) * 2010-07-14 2014-10-21 Nippon Kayaku Kabushiki Kaisha Photosensitive resin composition and cured product thereof
JP7160532B2 (ja) * 2015-03-20 2022-10-25 ブルー キューブ アイピー エルエルシー 硬化性組成物

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TW201708437A (zh) 2017-03-01
TWI700340B (zh) 2020-08-01
JP2018515630A (ja) 2018-06-14
US20180072900A1 (en) 2018-03-15
WO2016160346A1 (fr) 2016-10-06
US10442941B2 (en) 2019-10-15
JP6920205B2 (ja) 2021-08-18
EP3271429A1 (fr) 2018-01-24

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